ZSimpWin Version 3.

00

For Windows 98/2000/XP

Electrochemical Impedance Spectroscopy
Data Analysis Software




Technical Note 1:
Extrapolation using Kramers-Kronig relations


February 2001
Revised: January 1, 2002

written by
Bruno Yeum, Ph.D.
EChem Software
Ann Arbor, Michigan, USA










Tech Note 01- Extrapolation using KK relations 2

Technical Note 1:
Extrapolation using Kramers-Kronig relations

Bruno Yeum, Ph.D.
EChem Software
Revised: October 1, 2001

When ZSimpWin Version 2.00 was released in March, 2001, this feature was not fully developed. The
updates in this Note are applicable to V 2.10 and V 3.00.

1. Background

Theoretically, Z can be determined from Z using Eq. 1, if the data were available in the full frequency
range. Conversely, Z can be determined from Z using Eq. 2.






( 1)





(2)
Experimental difficulties in acquiring data in the low frequency region.

The contributions to the integrals of the K-K relations are very large in the region near the frequency
being evaluated. Without sufficient data in the low frequency region, it may not be possible to
calculate the data in the region with a reasonable accuracy.

2. Assumptions

1. No change of electrochemical system during measurement, i.e., the values of the electrical components
are constant.
2. Experimental data satisfy the K-K relations.

3. Conditions to be satisfied

1. Continuities in Z and Z
2. K-K relations.


4. Extrapolate Menu

Apply Kramers-Kronig: the work horse of this routine. Other menus are integrated into this routine.

Add points: Adds the extrapolated points to measured data.

Remove points: Removes the extrapolated points.

Calculate Impedance : After opening a file, calculate Z and Z using the K-K relations.

Save Extrapolated: Adds an extrapolated segment and then saves as a file.


Page Break

Tech Note 01- Extrapolation using KK relations 3

5. Apply Kramers-Kronig Dialog Box

This routine was developed using the algorithm described in the Reference. Extrapolate Z and Z below
the lowest measured frequency using polynomials of the same order.


Find: finds the order of the polynomials providing the least deviations of the extrapolated curves from the
calculated curves. Computations are performed for polynomials of different orders (4 to 8). Select this
request and click on the [OK] button.

View: displays the extrapolated curve associated with the order of the polynomials, and the lower bound of
the extrapolation frequency. The order is selected by clicking the Up or Down button in the Poly. order.
The lower bound is selected by clicking the radio button in the Frequency limit. It is also possible to
select a radio button in the Specifications representing a combination of the Poly. order and the
Frequency limit. Select this request and click on the [OK] button.

Evaluate: adds the extrapolated segment to the measured data, and then calculates Z and Z using the K-K
relations. Select this request and click on the [OK] button.

Print: Prints the results and displayed plot.

Copy: Copies the results to Windows clipboard.



6. Test Run Results

The order of the polynomials providing the best extrapolations were selected based on the value of the
(continuities) x (deviations).

Test File Name Order of
Polynomials
Capacitive term
At cut-off freq.
Effect of Extrapolations on
Deviations
ASTM0, 10 Hz to 1 kHz 6 Large Significant
ASTM0, 1 Hz to 1 kHz 6 Small Moderate
ASTM0, 0.1 Hz to 1 kHz 5 Very small Insignificant
ASTM0 - Negligible
Coated steel, 72h 7 Small Insignificant
Cylinder in NaCl 6 Large Significant
Steel, 72h 5 Moderate Moderate

Without extrapolations: Calculate impedance (Z and Z) using measured data Compare the
calculated curve with the measured data Determine the deviations.

Tech Note 01- Extrapolation using KK relations 4

With extrapolations: Extrapolate and append to measured data Calculate impedance (Z and Z)
using the extrapolated data Compare the extrapolated curve with calculated curve Determine the
deviations.
The best extrapolations = the order of the polynomials providing the minimum of the product,
(continuities) x (deviations).
When the capacitive term (Z) is large at the low cut-off frequency, extrapolations have significant
effects on reducing the deviations.

6.1. Impedance Calculation Routine

ASTM0
Theoretical data for Randles circuit. Evaluated the performance of the routine to compute Z and Z using
the K-K relations. After opening this file, selected Calculate Impedance in the Extrapolate Menu.













































Measured
ASTM0.txt
Model : Unknown Wgt : Modulus
Z ', ohm
120 110 100 90 80 70 60 50 40 30 20 10 0
- Z '', ohm
55
50
45
40
35
30
25
20
15
10
5
0
% Error, |Z|
Error, Angle

1E-05 1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 1E+02 1E+03 1E+04 1E+05 1E+06
%Error, |Z|
0.08
0.06
0.04
0.02
0
-0.02
-0.04
-0.06
-0.08
-0.1
Error, Angle
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
-0.05

Tech Note 01- Extrapolation using KK relations 5

The maximum error is about 0.1%. This indicates that impedance calculation routine is working properly.

For further testing, the data points were taken in the three frequency ranges a, b, and c and then
extrapolated using the routine.


6.2. Data with a large capaitive term at cut-off frequency

ASTM0, 10 Hz to 1 kHz
Because of the very large capacitive term, the calculated curve is much different from the data. The
deviation increases with decreasing the frequency.
























Measured
Calculated
ASTM0, 10 Hz to 1 kHz.txt
Applied Kramers-Kronig relations
Z ', ohm
90 80 70 60 50 40 30 20 10 0
- Z '', ohm
50
45
40
35
30
25
20
15
10
5
0

Tech Note 01- Extrapolation using KK relations 6






















































These data were extrapolated by two decades below the cut-off frequency. Extrapolated curves provided
much smaller deviations.
Z ', msd.
-Z '', msd.
ASTM0, 10 Hz to 1 kHz.txt
Model : Unknown Wgt : Modulus
Frequency, Hz
10 100 1,000
Z ' & - Z '', ohm
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
Extrapolated
Calculated
ASTM0, 10 Hz to 1 kHz, 6DUO.ext
Applied Kramers-Kronig relations
Z ', ohm
120 100 80 60 40 20 0
- Z '', ohm
60
55
50
45
40
35
30
25
20
15
10
5
0

Tech Note 01- Extrapolation using KK relations 7



























The extrapolated segments are very close to the corresponding truncated segments.


6.3. Data with small capacitive term at cut-off frequency

ASTM0, 1 Hz to 1 kHz






















The data points below 1 Hz were truncated and extrapolated by two decades below the frequency. The 5
th

order polynomials provided the best results.


Z ', Measured
Z ', Extrapolated
-Z '', Measured
-Z '', Extrapolated
ASTM0, 10 Hz to 1 kHz.txt
Selected spec. : 6DUO
Frequency, Hz
0.01 0.1 1 10 100 1,000
Z ' & - Z '', ohm
110
100
90
80
70
60
50
40
30
20
10
0
Z ', Measured
Z ', Extrapolated
-Z '', Measured
-Z '', Extrapolated
ASTM0, 1 Hz to 1 kHz.txt
Selected spec. : 7DUO
Frequency, Hz
0.01 0.1 1 10 100 1,000
Z ' & - Z '', ohm
110
100
90
80
70
60
50
40
30
20
10
0

Tech Note 01- Extrapolation using KK relations 8


ASTM0, 0.1 Hz to 1 kHz



























Capacitive term is very small at the truncation frequency. Extrapolations have insignificant effect in
reducing the deviations.
Z ', Measured
Z ', Extrapolated
-Z '', Measured
-Z '', Extrapolated
ASTM0, 0.1 Hz to 1 kHz.txt
Selected spec. : 5DUO
Frequency, Hz
1E-03 1E-02 1E-01 1E+00 1E+01 1E+02 1E+03
Z ' & - Z '', ohm
110
100
90
80
70
60
50
40
30
20
10
0

Tech Note 01- Extrapolation using KK relations 9

6.4. Extrapolation and Impedance Computation


Coated Steel, 72h

















































Z, Measured
Z, Extrapolated
Coated steel, 72h.txt
Selected spec. : 7DUO
Z ', ohm
40,000 30,000 20,000 10,000 0
-Z '', ohm
24,000
22,000
20,000
18,000
16,000
14,000
12,000
10,000
8,000
6,000
4,000
2,000
0
-2,000
Extrapolated
Calculated
Coated steel, 72h, 7DUO.ext
Applied Kramers-Kronig relations
Z ', ohm
40,000 30,000 20,000 10,000 0
- Z '', ohm
24,000
22,000
20,000
18,000
16,000
14,000
12,000
10,000
8,000
6,000
4,000
2,000
0
-2,000

Tech Note 01- Extrapolation using KK relations 10

Cylinder in NaCl

Because of the significant capacitive term at the low cut-off frequency, the impedance calculated using the
K-K relations is quite different from the data.




















































The 6
th
order polynomial provided the best results. Extrapolations substantially reduced the deviations.
The calculated curve is very close to the extrapolated curve.
Measured
Calculated
Cylinder in NaCl.txt
Applied Kramers-Kronig relations
Z ', ohm
350 300 250 200 150 100 50 0
- Z '', ohm
180
160
140
120
100
80
60
40
20
0
Z, Measured
Z, Extrapolated
Cylinder in NaCl.txt
Selected spec. : 6DUO
Z ', ohm
450 400 350 300 250 200 150 100 50 0
-Z '', ohm
240
220
200
180
160
140
120
100
80
60
40
20
0

Tech Note 01- Extrapolation using KK relations 11














































Z ', Measured
Z ', Extrapolated
-Z '', Measured
-Z '', Extrapolated
Cylinder in NaCl.txt
Selected spec. : 6DUO
Frequency, Hz
1E-03 1E-02 1E-01 1E+00 1E+01 1E+02 1E+03 1E+04 1E+05
Z ' & - Z '', ohm
450
400
350
300
250
200
150
100
50
0
Extrapolated
Calculated
Cylinder in NaCl, 6DUO.ext
Applied Kramers-Kronig relations
Z ', ohm
450 400 350 300 250 200 150 100 50 0
- Z '', ohm
240
220
200
180
160
140
120
100
80
60
40
20
0

Tech Note 01- Extrapolation using KK relations 12

Steel, 72h











































Z, Measured
Z, Extrapolated
Steel, 72h.txt
Selected spec. : 5DUO
Z ', ohm
10,000 8,000 6,000 4,000 2,000 0
-Z '', ohm
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
Z ', Measured
Z ', Extrapolated
-Z '', Measured
-Z '', Extrapolated
Steel, 72h.txt
Selected spec. : 5DUO
Frequency, Hz
1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 1E+02 1E+03 1E+04 1E+05
Z ' & - Z '', ohm
10,000
9,000
8,000
7,000
6,000
5,000
4,000
3,000
2,000
1,000
0

Tech Note 01- Extrapolation using KK relations 13


7. Additional Tests

The equivalent electrical circuits were taken from the Reference for testing. Simulation run results were
obtained, and then the test data were created by truncating data points for low and high frequencies. The
test data file name indicates the frequency below which data points were truncated. Data points in the high
frequency range were also truncated for some data. The order of the polynomials which provided good
results are indicated in the parentheses.

Simulation run Circuit Description Code Parameters Test data file (order of poly.)

TestA

R1(C2R3)
R1 = 10 ohms
C2 = 100 uF
R3 = 1e5 ohms

TestA, 1 mHz to 100 Hz (4)
TestA, 10 mHz to 100 Hz (7)


TestB


R1(C2(R3O4))
R1=10 ohms
C2 = 10 uF
R2 = 100 ohms
O4-Yo = 0.00612 S-sec^0.5
O4 -B = 1.22 sec^0.5


TestB, wmin = 1 Hz (7)

TestC

R1(Q2R3)
R1 = 1.87 ohms
Q2-Yo = 1100 uF
Q2-n = 0.71
R3 = 5.80 ohms
TestC, wmin = 1Hz (4)
TestC, wmin = 10 Hz (5)
TestC, wmin = 50 Hz (5)



TestD



R1(C2(R3O4(C5R6)))
R1 = 23 ohms
C2 = 19 uF
R3 = 418 ohms
O4-Yo = 9.96e-4 S-sec^0.5
O4-B = 0.843 sec^0.5
C5 = 95 uF
R6 = 695 ohms

TestD, 0.1 Hz to 1 kHz (7)
TestD, 1 Hz to 1 kHz (7)
TestD, 5 Hz to 1 kHz (8)

These data files are also located in the ...\data\kktest data folder. Find extrapolations and compare with
the simulation run results.


Summary

1. When the impedance below the lowest measured frequency seem to have a dominant effect on the
measured data, you may consider extrapolating the measured data and using the extrapolated data for
analysis.

2. It is not pertinent to test the validity of the measured data using the K-K relations without
extrapolations when capacitive term is significant at the low cut-off frequency (no data below this
frequency).

3. Standard procedure: (a) determine the extrapolations of the Z and Z satisfying the K-K relations, (b)
compare the extrapolated curves with corresponding calculated curves , and (c) determine the
deviations. If the deviations are very large, we may question the validity of the measured data.


Reference

J.M. Esteban and M.E. Orazem: "On the Application of the Kramers-Kronig Relations to Evaluate the
Consistency of Electrochemical Impedance Data," J. Electrochem. Soc., Vol. 138, No. 1, 1991, pp. 67-76.